CN115746186A - Acrylic prepolymer containing oxetane functional groups, preparation and application thereof - Google Patents
Acrylic prepolymer containing oxetane functional groups, preparation and application thereof Download PDFInfo
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- CN115746186A CN115746186A CN202211483722.8A CN202211483722A CN115746186A CN 115746186 A CN115746186 A CN 115746186A CN 202211483722 A CN202211483722 A CN 202211483722A CN 115746186 A CN115746186 A CN 115746186A
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Abstract
The invention relates to an acrylic prepolymer containing an oxetane functional group, which has an oxetane group in a side chain and an acrylate group in a terminal group and can be used as a macromonomer and/or a crosslinking agent for free radical curing and/or cationic curing at the same time. The invention also relates to a method for producing the oxetane-functional acrylic prepolymers of the invention and to the use thereof for free-radical and/or cationic curing.
Description
Technical Field
The invention belongs to the technical field of polymer chemistry and photocuring, and particularly relates to an oxetane functional group-containing acrylic prepolymer which can be used as a macromonomer and/or a crosslinking agent and is suitable for free radical curing and/or cationic curing. The invention also relates to the preparation of the oxetane-functional acrylic prepolymer and its use.
Background
The photo-curing techniques can be classified into radical curing, cationic curing, and hybrid radical/cationic curing according to mechanisms. Radical curing is the addition polymerization of unsaturated groups in the prepolymer and monomer by the radical generation of a photoinitiator under light irradiation. Cationic curing is the cationic initiator which generates protonic acid or Lewis acid under light irradiation to form a positive ion active center to initiate the ring opening polymerization of cations. Radical/cationic hybrid curing means that radical photopolymerization and cationic photopolymerization occur simultaneously in the same system. The above-mentioned radical and/or cation curing system, especially cation curing system, has the advantages of fast curing speed, many kinds of initiator, stable storage, etc., so that the industrial demand is strong, and it can be extensively used in light-cured paint, printing ink, photosensitive dry film resist and insulating coating. However, there are some problems and disadvantages, especially the disadvantages of few kinds of prepolymers or macromonomers, high price, and unadjustable performance of the cured product, etc. for the curing system, which limits the practical application in some specific fields.
Therefore, in recent years, those skilled in the art have made intensive studies on the synthesis and application of various monomers and prepolymers thereof, especially polyfunctional oxacycloalkane monomers and prepolymers, which are suitable for use in a photocurable system. For example, CN104447635a produces di-and tri-functional oxetane monomers by transesterification; EP3486238A1 prepares a series of oxetane-containing prepolymers by means of ring-opening polymerization of epoxy compounds and introduces epoxy groups at the end groups by subsequent modification by polymerization to obtain prepolymers with polyepoxide and oxetane groups; US2001002423A1 obtains copolymers having oxetanyl groups and fluorine atoms by free radical polymerization of vinyl monomers containing oxetanyl groups.
However, in general, the polyfunctional oxacycloalkane prepolymers known from the prior art still have poor control of the molecular weight and of the molecular weight distribution and also have disadvantages of high viscosity and inadequate flowability. In addition, in the prior art, multi-step organic synthesis reaction is needed for preparing the polyfunctional oxetane monomer and the prepolymer thereof, and the defects of complex treatment after reaction, byproduct generation and the like exist. Furthermore, the existing preparation of oxetane prepolymers mainly utilizes the conventional strategy of free radical polymerization or modification after polymerization, and has the problems of incomplete reaction, uneven product properties and the like.
In view of the above, research and development of multifunctional oxetane prepolymers having higher performance, particularly development of novel multifunctional oxetane prepolymers suitable for cationic curing and/or radical curing systems which are rapidly developed at present and having controllable molecular weights and low viscosities, are becoming the core research direction in this field.
Disclosure of Invention
In view of the problems of the prior art, the present inventors have conducted extensive and intensive studies on prepolymers suitable for use in cationically curing and/or radically curing systems, in order to find a novel polyfunctional oxetane-based prepolymer which can be suitably used in cationically curing and/or radically curing systems and has a controlled molecular weight and a low viscosity.
The inventors surprisingly found that a novel oxetane functional group-containing acrylic prepolymer having an oxetane group in a side chain and an acrylate group in a terminal group can be obtained by a one-step reaction by using an oxetane functional group-containing acrylic monomer and performing Catalytic Chain Transfer Polymerization (CCTP) using an organic cobalt complex as a catalytic chain transfer agent. Compared with the oxetane prepolymer obtained by the conventional free radical polymerization or post-polymerization modification strategy, the novel oxetane functional group-containing acrylic prepolymer provided by the invention has an oxetane group on the side chain and an acrylate group on the terminal group, and can be used as a macromonomer and/or a crosslinking agent to perform free radical curing and cationic curing respectively or simultaneously, so that the novel oxetane functional group-containing acrylic prepolymer can be used for free radical curing, cationic photocuring or free radical/cationic dual curing systems.
The object of the present invention is achieved based on the above findings.
It is therefore an object of the present invention to provide an oxetane-functional acrylic prepolymer having oxetane groups in the side chains and acrylate groups in the end groups, useful as free-radically and/or cationically curable macromonomers and/or crosslinkers.
In addition, the acrylic prepolymer containing oxetane functional groups provided by the invention has the following beneficial effects:
(1) The invention can regulate the molecular weight and viscosity of the obtained acrylic prepolymer containing the oxetane functional group, thereby obtaining the prepolymer with low molecular weight and narrow molecular weight distribution as well as low viscosity and excellent fluidity.
(2) The invention can regulate the content and density of the oxetanyl group in the obtained acrylic prepolymer containing the oxetanyl functional group, and can also regulate the physical properties of the prepolymer, such as glass transition temperature, thermal stability and the like. Thus, the oxetane functional group-containing acrylic prepolymers provided by the present invention can have a similar or greater number of oxetane groups than conventional di-, tri-or polyfunctional oxetane small molecule monomers and can provide higher crosslink density during polymerization.
(3) The invention adopts one-step reaction to avoid complex multistep organic synthesis reaction, thereby avoiding the problems of difficult synthesis, overhigh cost and the like of polyfunctional oxetane monomers and overcoming the defects of complicated treatment, byproduct generation and the like after multistep reaction.
Another object of the present invention is to provide a process for preparing the oxetane-functional acrylic prepolymer of the present invention.
It is a further object of the present invention to provide the use of the oxetane functional acrylic prepolymers of the present invention for free radical curing and/or cationic curing.
The technical scheme for achieving the purpose of the invention can be summarized as follows:
1. an acrylic prepolymer containing an oxetane functional group, characterized in that the side chain of the prepolymer has an oxetane group and the terminal group has an acrylate group.
2. A prepolymer according to embodiment 1, characterised in that the degree of polymerisation of the prepolymer is in the range 1 to 50, preferably 2 to 18, more preferably 3 to 15; and/or the presence of a gas in the gas,
the weight average molecular weight M of the prepolymer w Is 200-10000Da, preferably 500-8000Da, more preferably 600-5000Da; and/or the presence of a gas in the gas,
the polydispersity index (PDI) of the prepolymer is from 1.0 to 5.0, preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0.
3. A prepolymer according to embodiment 1 or 2 characterised in that the prepolymer is a homopolymer or a copolymer wherein the copolymer is a random, gradient or block copolymer.
4. A prepolymer according to any one of embodiments 1 to 3, characterised in that the prepolymer is a hyperbranched copolymer, wherein the side chains of the hyperbranched copolymer also have acrylate groups.
5. A prepolymer according to any one of embodiments 1 to 4 characterised in that the prepolymer is derived from the following monomers:
(A) A monomer of formula 1:
wherein
x is an integer from 1 to 3, preferably x is 1;
R 1 is H or CH 3 Preferably R 1 Is CH 3 (ii) a And
R 2 is H, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Hydroxyalkyl radical, C 1 -C 6 Alkoxy or C 1 -C 6 A haloalkoxy group; preferably R 2 Is H, halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Hydroxyalkyl radical, C 1 -C 4 Alkoxy or C 1 -C 4 A haloalkoxy group; more preferably R 2 Is H or C 1 -C 4 Alkyl, especially ethyl; and
(B) Optionally other (meth) acrylic or styrenic monomers; and
(C) Optionally di (meth) acrylate ester monomers of glycols.
6. A prepolymer according to embodiment 5 characterised in that the monomer (A) is (3-ethyloxetan-3-yl) methyl methacrylate.
7. A prepolymer according to embodiment 5 or 6 characterised in that the monomer (B), if present, is one or more selected from the group consisting of: acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, benzyl acrylate and derivatives thereof, benzyl methacrylate and derivatives thereof, styrene and derivatives thereof; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate are preferred; more preferably methyl methacrylate and/or butyl methacrylate; and/or the presence of a gas in the gas,
if present, the mass ratio of monomer (B) to the sum of the other monomers is 1:1-1:5, preferably 1:1-1:3, more preferably 1:1.
8. A prepolymer according to any one of embodiments 5 to 7 characterised in that the monomer (C), if present, is one or more selected from the group consisting of: ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, and tripropylene glycol dimethacrylate; preferably ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate and tripropylene glycol dimethacrylate; more preferably ethylene glycol dimethacrylate; and/or
If present, the mass ratio of monomer (C) to the sum of the other monomers is 1:3-1, 20, preferably 1:4-1, 10, more preferably 1:5.
9. A process for the preparation of a prepolymer according to any of embodiments 1 to 8, characterised in that monomer (a) and optionally monomer (B) and optionally monomer (C) are subjected to a one-shot Catalysed Chain Transfer Polymerisation (CCTP) reaction in the presence of a chain transfer agent and a free radical initiator.
10. The process according to embodiment 9, characterized in that the chain transfer agent is one or more selected from the group consisting of: bis [ (difluoroboron) dimethylglyoximato)]Cobalt (II) (bis [ (fluorobionyl) dimethyl glyoximato)]cobalt (II), coBF), bis [ (difluoroboron) dimethylphenyl glyoximato]Cobalt (II) (bis [ (fluoroyl) dimethyl-phenoxy-glyoximato)]cobalt (II), co (MePh) BF), bis [ (difluoroboron) diphenylglyoxime radical]Cobalt (II) (bis [ (fluorobionyl) diphenylglyoximato]cobalt (II), coPhBF), bis [ dimethylglyoxime]Cobalt (II) (bis [ dimethyl glyoximato)]cobalt(II)，Co(dmg) 2 ) [ meso-tetraphenylporphyrin ]]Cobalt (meso-Ph 4-porphin), coP, tetramethylether-type cobalt hematoporphyrin (tetramethylether of cobalt hematoporphyrin IX, coTMHP), tetrafluorophenyl cobalt porphyrin (cotfp), bis [ (difluoroboron) dimethylglyoximato]Isopropylpyridinium cobalt (II) (bis [ (fluorobionyl) dimethyl glyoximate]isoproyl pyridine cobalt (II), co (ipp) BF) and 2,16-bis (4-butanamido) cobalt (II) phthalocyanine (cobalt (II) 2,16-bis (4-butanamido) phthalocyanine, coPc), preferably bis [ (difluoroboryl) dimethylglyoximato]Cobalt (II) (CoBF); and/or the presence of a gas in the gas,
the chain transfer agent is used in an amount of 0.1 to 100ppm, preferably 1 to 80ppm, more preferably 5 to 50ppm, based on the total weight of the monomers.
11. The process according to embodiment 9 or 10, characterized in that the radical initiator is one or more selected from the group consisting of: ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyronitrile formamide, dibenzoyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide, preferably azobisisobutyronitrile; and/or
The free-radical initiators are used in amounts of from 0.1 to 8% by weight, preferably from 0.1 to 4% by weight, more preferably from 0.3 to 2% by weight, based on the total weight of the monomers.
12. The process according to any of embodiments 9 to 11, characterized in that the reaction temperature is 50 to 120 ℃, preferably 55 to 100 ℃, more preferably 60 to 80 ℃.
13. The process according to any of embodiments 9 to 12, characterized in that the one-step Catalytic Chain Transfer Polymerization (CCTP) reaction is carried out in a polymerization manner of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or precipitation polymerization.
14. Use of a prepolymer obtained according to any one of embodiments 1 to 8 or according to the process of any one of embodiments 9 to 13 in radical curing and/or cationic curing.
15. A photocurable composition comprising the prepolymer of any one of embodiments 1-8 or obtained according to the process of any one of embodiments 9-13.
16. A cured material obtainable from the photocurable composition of embodiment 15.
17. A method for preparing a photocurable material comprising irradiating the photocurable composition of embodiment 15 with ultraviolet light, visible light, or laser light.
Description of the drawings:
FIG. 1 is a GPC chart of a prepolymer (homopolymer A1) of the present invention prepared according to example 1.
FIG. 2 is a GPC chart of a prepolymer of the present invention (homopolymer A2) prepared according to example 2.
FIG. 3 is a GPC chart of a prepolymer of the invention (hyperbranched copolymer A5) prepared according to example 5.
FIG. 4 is a nuclear magnetic spectrum of a prepolymer of the invention (homopolymer A1) prepared according to example 1.
FIG. 5 is a nuclear magnetic spectrum of a prepolymer of the invention (hyperbranched copolymer A5) prepared according to example 5.
FIG. 6 is a MALDI-ToF MS spectrum of a prepolymer of the invention (homopolymer A2) prepared according to example 2.
FIG. 7 is a comparative graphical representation of the surface topography and water flux bars of PVDF-based ultrafiltration membrane photocuring experiments testing prepolymers of the present invention (homopolymer A1, copolymer A3) prepared according to examples 1 and 3.
FIG. 8 is a graphic representation of the visual effect of a test of a Petri dish photocuring experiment of a prepolymer of the invention (hyperbranched copolymer A5) prepared according to example 5.
FIG. 9 is an IR spectrum of a Petri dish photocuring experiment test of a prepolymer of the invention (hyperbranched copolymer A5) prepared according to example 5.
Detailed Description
According to one aspect of the present invention, there is provided an acrylic prepolymer having an oxetanyl group in a side chain, and an acrylate group in a terminal group.
Specifically, the prepolymer of the present invention has both an oxetanyl group in a side chain and an acrylate group in a terminal group, and thus can be used as a macromonomer and/or a crosslinking agent for radical curing and cationic curing, respectively or simultaneously, and thus can be used for radical curing, cationic photocuring or radical/cationic dual curing systems.
According to a preferred aspect of the invention, the prepolymers of the invention are derived from the following monomers:
(A) A monomer of formula 1:
wherein
x is an integer of 1 to 3;
R 1 is H or CH 3 (ii) a And
R 2 is H, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Hydroxyalkyl radical, C 1 -C 6 Alkoxy or C 1 -C 6 A haloalkoxy group; and
(B) Optionally other (meth) acrylic or styrenic monomers; and
(C) Optionally di (meth) acrylate ester monomers of glycols.
In the present invention, the term "acrylic" means acrylate or methacrylate esters or derivatives and combinations thereof containing acrylic groups. The expression "acrylate group" alone is understood to include both acrylate and methacrylate groups.
In the present invention, the prefix "C n -C m "in each case denotes that the number of carbon atoms contained in the radical is n to m.
"halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises fluorine, chlorine or a combination thereof.
The term "C" as used herein n -C m Alkyl "means a branched or unbranched saturated hydrocarbon radical having n-m, for example 1-6, preferably 1-4, carbon atoms. C 1 -C 6 Alkyl can be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl. C 1 -C 4 Alkyl groups may be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
The term "C" as used herein n -C m Haloalkyl "means C substituted with one or more halogen atoms which may be the same or different n -C m Alkyl radicals, e.g. C 1 -C 6 Haloalkyl, preferably C 1 -C 4 A haloalkyl group. As C n -C m Examples of haloalkyl radicals which may be mentioned are the monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, dichloromethylethyl, monochlorobutyl, dichloromethylpropyl, trichloromethylpropyl, monochloropentyl, dichloromethylbutyl, monochlorohexyl and isomers thereof, in particular the 1-chloromethylpropyl, 1,1-dichloromethylethyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 2,2-dichloromethylpropyl, 1,1,2-trichloromethylpropyl and 1,2,2-trichloromethylpropyl radicals.
The term "C" as used herein n -C m Hydroxyalkyl "means at C n -C m Open chain C corresponding to alkyl n -C m C having a hydroxy group bonded to any carbon atom of the alkane n -C m Alkyl radicals, e.g. C 1 -C 6 Hydroxyalkyl, particularly preferably C 1 -C 4 Hydroxyalkyl radicals, such as the hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and isomers thereof, in particular the hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-tert-butyl, hydroxy-n-pentyl and hydroxy-n-hexyl radical.
The term "C" as used herein n -C m Alkoxy "means at C n -C m Open chain C corresponding to alkyl n -C m C having an oxygen atom as a linking group bonded to any carbon atom of the alkane n -C m Alkyl radicals, e.g. C 1 -C 6 Alkoxy, more preferably C 1 -C 4 An alkoxy group. C 1 -C 6 Alkoxy can be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, n-pentoxy, isopentoxy and n-hexoxy. C 1 -C 4 Alkoxy can be methoxy, ethoxy, propoxy, butoxy and isomers thereof, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy.
The term "C" as used herein n -C m Haloalkoxy "means C substituted by one or more of the same or different halogen atoms n -C m Alkoxy radicals, e.g. C 1 -C 6 Haloalkoxy, preferably C 1 -C 4 A haloalkoxy group. As C n -C m Examples of haloalkoxy groups which may be mentioned are monochlorooxy, 2-chloroethoxy, 3-chloropropoxy, 4-chlorobutoxy, 5-chloropentyloxy, 6-chlorohexyloxy and isomers thereof, in particular monochlorooxy, 2-chloroethoxy, 3-chloro-n-propoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy, 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloro-n-pentyloxy, 4-chloroisopentyloxy and 6-chloro-n-hexyloxy.
In some embodiments of the invention, R 2 Usually H, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Hydroxyalkyl radical, C 1 -C 6 Alkoxy or C 1 -C 6 A haloalkoxy group. Preferably, R is 2 Is H, halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Hydroxyalkyl radical, C 1 -C 4 Alkoxy or C 1 -C 4 A haloalkoxy group. It is particularly preferred that R 2 Is H or C 1 -C 4 An alkyl group. For example, R 2 Can be H, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy-tert-butyl.
In a particularly preferred embodiment of the invention, R 2 Is ethyl.
In a preferred embodiment of the invention, x is 1.
In a preferred embodiment of the invention, R 1 Is CH 3 。
In a particularly preferred embodiment of the present invention, monomer (A) is (3-ethyloxetan-3-yl) methyl methacrylate.
In a preferred embodiment of the present invention, the prepolymer of the present invention may further comprise monomer (B) other (meth) acrylic or styrenic monomers. Thus, the prepolymer of the present invention may be a homopolymer or a copolymer, wherein the copolymer may be a random, gradient, or block copolymer.
In a preferred embodiment of the present invention, the monomer (B), if present, is one or more selected from the group consisting of: acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, benzyl acrylate and derivatives thereof, benzyl methacrylate and derivatives thereof, styrene and derivatives thereof.
In a more preferred embodiment of the present invention, the monomer (B), if present, is one or more selected from the group consisting of: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate.
In a particularly preferred embodiment of the present invention, the monomers (B), if present, are methyl methacrylate and/or butyl methacrylate.
In a further preferred embodiment of the invention, the mass ratio of monomer (B), if present, to the sum of the other monomers is 1:1-1:5, preferably 1:1-1:3, more preferably 1:1.
In a preferred embodiment of the present invention, the prepolymer of the present invention may further comprise monomer (C) di (meth) acrylate ester monomer of other glycol. The prepolymers of the invention may therefore also be hyperbranched copolymers, where the side chains of the hyperbranched copolymers also have acrylate groups.
In a preferred embodiment of the present invention, the monomer (C), if present, is one or more selected from the group consisting of: ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, and tripropylene glycol dimethacrylate.
In a more preferred embodiment of the present invention, the monomer (C), if present, is one or more selected from the group consisting of: ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, and tripropylene glycol dimethacrylate.
In a particularly preferred embodiment of the present invention, monomer (C), if present, is ethylene glycol dimethacrylate.
In yet another preferred embodiment of the present invention, the mass ratio of monomer (C) to the sum of the other monomers, if present, is 1:3-1, 20, preferably 1:4-1, more preferably 1:5.
In some embodiments of the invention, the invention provides prepolymers of low molecular weight and narrow molecular weight distribution. Specifically, the polymerization degree of the prepolymer is 1 to 50, preferably 2 to 18, more preferably 3 to 15. The weight average molecular weight M of the prepolymer w Is 200-10000Da, preferably 500-8000Da, more preferably 600-5000Da. The polydispersity index (PDI) of the prepolymer is from 1.0 to 5.0, preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0.
According to another aspect of the present invention there is provided a process for the preparation of the prepolymer of the present invention which comprises subjecting monomer (a) and optionally monomer (B) and optionally monomer (C) to a one-shot Catalysed Chain Transfer Polymerisation (CCTP) reaction in the presence of a chain transfer agent and a free radical initiator.
Catalytic Chain Transfer Polymerization (CCTP) is a recently discovered free radical polymerization process that employs an organic cobalt complex as a catalytic chain transfer agent. The chain transfer agent, the organic cobalt complex, has a very high chain transfer constant, which allows the hydrogen in the formed radical chain to be transferred to another olefin, thereby forming a macromolecule with an unsaturated bond at the end, and the double bond at the end has enough activity to perform a cleavage-addition or radical polymerization reaction with a special monomer.
In the method of the present invention, the polymerization is completed under prescribed conditions by catalyzing the chain transfer polymerization (CCTP) reaction using a one-step method, i.e., simultaneously adding the monomer (a) and optionally the monomer (B) and optionally the monomer (C), a chain transfer agent and a radical initiator to the reaction system.
In the one-step Catalytic Chain Transfer Polymerization (CCTP) reaction of the present invention, the chain transfer agent is one or more selected from the group consisting of: bis [ (difluoroboron) dimethylglyoximato)]Cobalt (II) (bis [ (fluorobionyl) dimethyl glyoximato)]cobalt (II), coBF), bis [ (difluoroboryl) dimethylphenyl glyoximato]Cobalt (II) (bis [ (fluoroyl) dimethyl-phenoxy-glyoximato)]cobalt (II), co (MePh) BF), bis [ (difluoroboron) diphenylglyoxime radical]Cobalt (II) (bis [ (fluorobionyl) diphenylglyoximato]cobalt (II), coPhBF), bis [ dimethylglyoximato]Cobalt (II) (bis [ dimethyl glyoximato)]cobalt(II)，Co(dmg) 2 ) [ meso-tetraphenylporphyrin ]]Cobalt (meso-Ph 4-porphin), coP, tetramethylether-type cobalt hematoporphyrin (tetramethylether of cobalt hematoporphyrin IX, coTMHP), tetrafluorophenyl cobalt porphyrin (cotfp), bis [ (difluoroboron) dimethylglyoximato]Isopropylpyridinium cobalt (II) (bis [ (fluorobionyl) dimethyl glyoximate]isoproyl pyridine cobalt (II), co (ipp) BF) and 2,16-bis (4-butylamido) cobalt (II) phthalocyanine (cobalt (II) 2,16-bis (4-butanamido) phthalocyanine, coPc).
In a preferred embodiment of the present invention, the chain transfer agent is bis [ (difluoroboron) dimethylglyoximato ] cobalt (II) (CoBF).
In some embodiments of the invention, the chain transfer agent is used in an amount of 0.1 to 100ppm, preferably 1 to 80ppm, more preferably 5 to 50ppm, such as 1ppm, 3ppm, 5ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 80ppm, based on the total weight of the monomers.
In the one-step Catalytic Chain Transfer Polymerization (CCTP) reaction of the present invention, the radical initiator is one or more selected from the group consisting of: ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyronitrile, dibenzoyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide.
In a preferred embodiment of the present invention, the radical initiator is azobisisobutyronitrile.
In some embodiments of the invention, the free radical initiator is used in an amount of 0.1 to 8 wt.%, preferably 0.1 to 4 wt.%, more preferably 0.3 to 2 wt.%, such as 0.1 wt.%, 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 3.0 wt.% and 4.0 wt.%, based on the total weight of the monomers.
The one-step Catalyzed Chain Transfer Polymerization (CCTP) reaction described above is generally carried out in a solvent, preferably an organic solvent. There is no particular limitation in the choice of the type of solvent, as long as it is suitable for use in a one-step Catalytic Chain Transfer Polymerization (CCTP) reaction and is chemically inert to the reaction participants, i.e., does not participate in the Catalytic Chain Transfer Polymerization (CCTP) reaction. Suitable solvents may for example be one or more selected from the group consisting of: methanol, ethanol, propanol, isopropanol, acetonitrile, butanone, toluene, propylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol ethyl ether, and ethylene glycol methyl ether. As an example of the solvent, acetonitrile is generally employed. Further, the amount of the solvent to be used is not particularly limited, and those skilled in the art can select an appropriate amount according to the practical scale of the reaction.
In some embodiments of the invention, the temperature range of the one-step Catalyzed Chain Transfer Polymerization (CCTP) reaction is typically 50-120 deg.C, preferably 55-100 deg.C, more preferably 60-80 deg.C, such as 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C and 100 deg.C. The reaction time is not particularly limited, and usually 1 to 20 hours, preferably 1 to 12 hours.
Furthermore, the process is generally carried out under an inert atmosphere. There is no particular limitation in the selection of the type of inert gas, so long as it is chemically inert to the entire reaction system. As an example of the inert gas, nitrogen gas is usually used.
For the purposes of the present invention, the one-step Catalyzed Chain Transfer Polymerization (CCTP) reaction may be carried out by bulk, solution, emulsion, suspension or precipitation polymerization. The feeding method is also not particularly limited, and may be carried out by a one-shot feeding method, a semi-continuous feeding method and a continuous feeding method known to those skilled in the art, depending on the practical scale of the reaction.
After completion of the one-step Catalyzed Chain Transfer Polymerization (CCTP) reaction, the oxetane functional group-containing acrylic prepolymer product of the present invention is obtained. In general, if it is desired to further increase the purity of the reaction product, the reaction product may be further purified and, if desired, may optionally be subjected to a work-up treatment, for example to remove residual organic solvents. The means for removing the organic solvent is not particularly limited, and the organic solvent can be removed by distillation under reduced pressure. After removing the residual organic solvent, the product can be optionally precipitated in a solvent, thereby removing residual monomers and other small molecular substances to obtain a product with higher purity. The choice of the solvent is conventional and is not particularly limited. According to the invention, the reaction product is advantageously treated with a mixture of methanol and water.
The side chain of the acrylic prepolymer containing the oxetane functional group provided by the invention has the oxetane group and the terminal group has the acrylate group, and the acrylic prepolymer can be used as a macromonomer and/or a crosslinking agent to carry out free radical curing and cationic curing respectively or simultaneously. The present invention therefore also provides for the use of the oxetane-functional acrylic prepolymers of the invention in free radical curing and/or cationic curing. In addition, the prepolymer disclosed by the invention has the advantages of low molecular weight, narrow molecular weight distribution, low viscosity, good fluidity and the like. Furthermore, compared with the conventional di-, tri-or multifunctional oxetane small molecule monomer, the oxetane functional group-containing acrylic prepolymer provided by the invention can have the number of oxetane groups similar to or more than that of the conventional di-, tri-or multifunctional oxetane small molecule monomer, can provide higher crosslinking density in the polymerization process, so that the curing reaction can be effectively carried out, and in addition, the prepolymer has good matching property with a wide-range light source of ultraviolet light, visible light or laser, so that the oxetane functional group-containing acrylic prepolymer can be better applied to the fields of special coatings, inks, microelectronics, 3D printing and printing with higher requirements. In addition, the prepolymer preparation of the invention avoids complex multi-step organic synthesis reaction, thereby overcoming the defects of complex post-treatment, byproduct generation and the like of multi-step reaction, and being very suitable for industrial production.
Thus, according to a further aspect of the present invention, there is provided a photocurable composition comprising the oxetane-functional acrylic prepolymer of the present invention as a polymerizable macromer or prepolymer. The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, or the like. The photocurable composition may comprise, in addition to the prepolymer of the invention, a free-radical photoinitiator and/or a cationic photoinitiator and optionally further monomers or oligomers containing vinyl ether double bonds, cycloaliphatic epoxy groups or oxirane groups or the like groups which can participate in free-radical and/or cationic photocuring, such as 3-methyl-3-hydroxymethyloxetane (MOXE), 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylmethyl ester (AOO) or 4-Vinylepoxycyclohexane (VOH).
As the photoinitiator for cationic photocuring, iodine is commonly used
Salt and sulfur
And (3) salt. For example, one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylthio
Hexafluorophosphate, 4- (phenylthio) phenyl-diphenylsulfide
Hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfur
Hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfur
Hexafluoroantimonate, diphenyl iodide hexafluorophosphate
Salt, 4-octyloxy diphenyl iodide
Hexafluorophosphate, 4-octyloxy diphenyliodine
Hexafluoroantimonate, 4-isobutylphenyl-4' -methylphenyliodide
Hexafluorophosphate, 4-isobutylphenyl, 4' -methylphenyliodide
Hexafluoroantimonate and bis (4-dodecylbenzene) iodide
Hexafluoroantimonate and bis (4-dodecylbenzene) iodide
Hexafluorophosphate, bis (4-tert-butylbenzene) iodide
Hexafluorophosphate or bis (4-tert-butylphenyl) iodide
Hexafluoroantimonate; preferred is 4- (phenylthio) phenyl-diphenylthio
Hexafluorophosphate, 4- (phenylthio) phenyl-diphenylsulfide
Hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfur
Hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfur
Hexafluoroantimonate, diphenyl iodide hexafluorophosphate
Salt, 4-octyloxy diphenyl iodide
Hexafluorophosphate and 4-octyloxy diphenyliodine
Hexafluoroantimonate; in particular 4- (phenylthio) phenyl-diphenylthio
A hexafluorophosphate salt.
As photoinitiators for free-radical photocuring, mono-or bisacylphosphine oxides, phenones, benzoin and benzils are frequently used. For example, one or more selected from the group consisting of phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphosphonic acid ethyl ester, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone, methyl benzoylformate, benzophenone, benzil, benzoin, α -diethoxy acetophenone, 4-methylbenzophenone, 4,4 '-bis (dimethylamino) benzophenone, 4,4' -bis (diethylamino) benzophenone, and 2,4,6-trimethylbenzophenone; preferably 2-hydroxy-2-methyl-1-phenylacetone, α -diethoxyacetophenone, 4-methylbenzophenone, 4,4 '-bis (dimethylamino) benzophenone, 4,4' -bis (diethylamino) benzophenone and 2,4,6-trimethylbenzophenone; especially 2-hydroxy-2-methyl-1-phenylacetone.
The photocurable composition of the present invention may also contain a sensitizer. As sensitizers, mention may be made, for example, of benzophenones and derivatives thereof, such as 4- (4-methylphenylthio) benzophenone or 4,4' -bis (diethylamino) benzophenone, thioxanthones and derivatives thereof, such as 2-isopropylthioxanthone, anthraquinones and derivatives thereof, such as 2-ethylanthraquinone, coumarin derivatives, such as 5,7-dimethoxy-3- (4-dodecylbenzoyl) coumarin, camphorquinone, phenothiazine and derivatives thereof, 3- (aroylmethylene) thiazoline, rhodanine and derivatives thereof, eosin, rhodamine, acridine, anthocyanidin, merocyanine dyes; benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and derivatives thereof are preferred, and 2-isopropyl thioxanthone is particularly preferred.
The photocurable composition of the present invention may also optionally comprise an organic solvent. The choice of organic solvent is conventional. As the organic solvent, aromatic hydrocarbons such as benzene, toluene, haloalkanes such as chloroform, dichloromethane, ethyl chloride, ketones such as acetone, butanone, pentanone and the like, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, and glycol ethers, glycol ether acetates, propylene glycol ethers, propylene glycol ether acetates and the like can be mentioned.
The photocurable composition of the present invention may also optionally contain other additives such as leveling agents, antioxidants, anti-settling agents, colorants, biocides, and thermal insulation additives, among others.
The preparation of the photocurable composition of the present invention and the amounts of the various components are conventional and generally the components of the photocurable composition of the present invention are mixed together homogeneously in the usual amounts.
Thus, in another aspect, the present invention also provides cured materials obtainable from the photocurable compositions of the present invention. The resulting cured material may be a photocurable coating, including coatings containing functional materials, coatings for ultraviolet, visible, or laser filters; a sealant; photoetching materials; a holographic recording material; 3D printing materials; a lithographic material; the preparation material of the optical device and the material for improving the mechanical property, such as carbon fiber composite material and/or inorganic nano particles and/or organic nano particles, etc.
Furthermore, the present invention relates to a process for preparing photocurable materials, which comprises irradiating the photocurable compositions of the present invention with ultraviolet light, visible light or laser light. The photocuring conditions are not particularly limited as long as the photocurable composition of the present invention can be photocured. The photocuring material has the advantages of good curing density, high curing speed, contamination resistance, good heat resistance and the like due to the fact that the prepolymer is used as the photocuring prepolymer or the macromonomer and/or the crosslinking agent.
Examples
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The specific techniques or conditions are not indicated in the examples, and are performed according to the techniques or conditions or product specifications described in the literature in the field.
The materials and reagents used in the examples described below are listed in Table A, and other materials and reagents are commercially available.
TABLE A-Experimental materials and reagents
The equipment used in the examples below is listed in Table B.
TABLE B-Experimental apparatus
| Name of the instrument | Instrument type | Manufacturer of the product |
| Real-time infrared spectrometer | Nicolet 5700 | Thermo Electron Co, USA |
| Nuclear magnetic resonance apparatus (NMR) | Avance 400M | Bruker, germany |
| Mass Spectrometer (MS) | Microflex LRF | Bruker Germany |
| Gel Permeation Chromatograph (GPC) | Waters707 | Waters corporation of America |
| Electronic balance | AR1140 | OHAUS corporation |
| Rotary evaporator | RE-52 | Shanghai Yarong biochemical instrument factory |
| Scanning Electron Microscope (SEM) | S4800 type | Hitachi Co of Japan |
Example 1 preparation of a prepolymer (homopolymer A1) according to the invention
Under the protection of inert gas and nitrogen, 50g of (3-ethyloxetan-3-yl) methyl methacrylate, 100ml of acetonitrile, 1g of azobisisobutyronitrile (azobisisobutyronitrile), a radical initiator and 50ppm of a chain transfer agent CoBF were added to a reaction vessel equipped with a mechanical stirrer, mixed well with stirring, heated to 60 ℃ and polymerized at 60 ℃ for 12 hours. Thereafter, acetonitrile was distilled off under reduced pressure to obtain a liquid homopolymer A1. For further purification of the product, the product may be precipitated in a mixed solvent of methanol and water (1:1 by volume), thereby removing residual small molecular substances such as monomers.
Example 2 preparation of a prepolymer according to the invention (homopolymer A2)
Under the protection of inert gas and nitrogen, 50g of (3-ethyloxetan-3-yl) methyl methacrylate, 100ml of acetonitrile, 1g of azobisisobutyronitrile (azobisisobutyronitrile), a radical initiator, and 5ppm of a chain transfer agent CoBF were added to a reaction vessel equipped with a mechanical stirrer, mixed well with stirring, heated to 60 ℃ and polymerized at 60 ℃ for 12 hours. Thereafter, acetonitrile was distilled off under reduced pressure to obtain a liquid homopolymer A2. For further purification of the product, the product may be precipitated in a mixed solvent of methanol and water (1:1 by volume), thereby removing residual small molecular substances such as monomers.
Example 3 preparation of a prepolymer of the invention (copolymer A3)
Under the protection of inert gas and nitrogen, 25g of (3-ethyloxetan-3-yl) methyl methacrylate, 25g of methyl methacrylate, 100ml of acetonitrile, 1g of Azobisisobutyronitrile (AIBN), a radical initiator and 50ppm of CoBF chain transfer agent were added to a reaction vessel equipped with a mechanical stirrer, mixed well by stirring, heated to 60 ℃ and polymerized at 60 ℃ for 12 hours. Thereafter, acetonitrile was removed by distillation under reduced pressure to obtain a liquid copolymer A3. For further purification of the product, the product may be precipitated in a mixed solvent of methanol and water (1:1 by volume), thereby removing residual small molecular substances such as monomers.
Example 4 preparation of a prepolymer of the invention (copolymer A4)
Under the protection of inert gas and nitrogen, 25g of (3-ethyl oxetan-3-yl) methyl methacrylate, 25g of butyl methacrylate, 100ml of acetonitrile, 1g of Azobisisobutyronitrile (AIBN), a free radical initiator and 5ppm of a chain transfer agent CoBF were added to a reaction vessel equipped with a mechanical stirrer, stirred to be mixed thoroughly, heated to 60 ℃ and polymerized at 60 ℃ for 12 hours. Thereafter, acetonitrile was distilled off under reduced pressure to obtain a liquid copolymer A4. For further purification of the product, the product may be precipitated in a mixed solvent of methanol and water (1:1 by volume), thereby removing residual small molecular substances such as monomers.
Example 5 preparation of a prepolymer of the invention (hyperbranched copolymer A5)
Under the protection of inert gas and nitrogen, 25g of (3-ethyl oxetan-3-yl) methyl methacrylate, 5g of ethylene glycol dimethacrylate, 100ml of acetonitrile, 1g of azobisisobutyronitrile as a radical initiator and 5ppm of a chain transfer agent CoBF were added to a reaction vessel equipped with a mechanical stirrer, stirred to be mixed well, heated to 60 ℃ and polymerized at 60 ℃ for 12 hours. Then, acetonitrile is removed by reduced pressure distillation, and the liquid hyperbranched copolymer A5 can be obtained. For further purification of the product, the product may be precipitated in a mixed solvent of methanol and water (1:1 by volume), thereby removing residual small molecular substances such as monomers.
Characterization and Performance test results
1. Molecular weight and PDI measurements
The weight-average molecular weight (M) in terms of polystyrene was measured by gel permeation chromatography (Waters: waters 707) w ) And number average molecular weight (M) n ) The measurement results are shown in Table 1 and FIGS. 1 to 3.
Specifically, the product prepared in the above example was dissolved in N, N-Dimethylformamide (DMF) at a concentration of 4000ppm, and then 100. Mu.l was injected into GPC. The mobile phase of GPC was flowed in at a flow rate of 1.0ml/min using tetrahydrofuran, and analyzed at 35 ℃. Four of Waters HR-05, 1,2 and 4E were connected in series as a chromatography column. The assay was performed using an RI detector and a PAD detector at 35 ℃. Meanwhile, the polydispersity index (PDI) is calculated by dividing the measured weight average molecular weight by the number average molecular weight.
TABLE 1 molecular weight and molecular weight distribution data for prepolymers
The results show that: the method can effectively regulate and control the molecular weight of the obtained acrylic prepolymer containing the oxetane functional group, thereby obtaining the prepolymer with low molecular weight, narrow molecular weight distribution, low viscosity and excellent fluidity. Furthermore, it can be seen from a comparison of example 1 with example 2 that by controlling the amount of chain transfer agent added, the molecular weight of the prepolymer tends to decrease as the amount of catalyst CoBF increases.
2. Nuclear magnetic characterization and mass spectrometry results
The prepolymer of the invention prepared in example 1 (homopolymer A1) was subjected to nuclear magnetic resonance examination, and the results are shown in FIG. 4. By analysis and comparison, it can be seen that: the characteristic peak of (3-ethyloxetan-3-yl) methyl methacrylate exists, wherein the characteristic peak of methylene in oxetane can be obviously seen (chemical shift is about 4.5 ppm); the characteristic peaks of the terminal acrylate double bonds (chemical shifts around 5.0-6.5 ppm) are also clearly visible. In addition, the prepolymer of the invention (hyperbranched copolymer A5) prepared in example 5 was also subjected to nuclear magnetic resonance detection, and the results are shown in FIG. 5. Similarly, it can be seen that the peak characteristic of the acrylate double bond (chemical shift of about 5.5 to 6.5 ppm) and the peak characteristic of the methylene group (chemical shift of about 4.5 ppm).
MALDI-ToF MS detection was performed on the prepolymer of the invention prepared in example 2 (homopolymer A2), and the results are shown in FIG. 6. As can be seen by analytical comparison, the prepolymer has typical peaks of (3-ethyloxetan-3-yl) methyl methacrylate prepolymer, the molecular weight is mainly concentrated between 600 and 3000Da, the peak distance is the mass of (3-ethyloxetan-3-yl) methyl methacrylate monomer, and the analysis of the typical peaks can deduce the degree of polymerization (DP = 5) and the precise structure of the (3-ethyloxetan-3-yl) methyl methacrylate prepolymer.
3. Results of photocuring effect analysis
PVDF-based ultrafiltration membrane photocuring experimental test
In order to verify the specific effect of the prepolymer participating in the photocuring reaction, the cationic photocuring reaction is carried out on the surface of the PVDF-based ultrafiltration membrane. The photocuring reaction adopts oxetane small molecule 3-methyl-3-hydroxymethyl oxetane (MOXE), prepolymer (homopolymer A1 and copolymer A3) and alicyclic epoxy compound 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylformate (AOO). Firstly, the compound is mixed with a cationic photoinitiator 4- (phenylthio) phenyl diphenyl sulfide
Hexafluorophosphate was dissolved in methanol, and then the PVDF membrane was soaked in the above methanol solution for 10min, followed by irradiation under a 365nm ultraviolet lamp for 10min. The ratio of the photo-curing reactants and the partial raw material structure are shown in Table 2.
TABLE 2 proportion of reactants for cationic photocuring on PVDF membrane surface
A series of parallel light curing experiments on the surface of the PVDF membrane are carried out to obtain membranes M1-M4, and the water flux and the surface morphology are tested, and the results are shown in FIG. 7. It can be seen from the analysis comparison that the photocuring modified films M2, M3, M4 have smaller water flux in the photocuring experiments with the addition of the prepolymer (homopolymer A1, copolymer A3) of the present invention relative to the PVDDF original film. This indicates that the prepolymer can act as a crosslinker, giving the photocurable coating a more dense structure. Surface morphology characterization is carried out on the PVDF original film and the photocuring modified films M1-M4 through a scanning electron microscope, and the surface pore structures of the films M2, M3 and M4 are obviously reduced relative to the original film in a photocuring experiment added with the prepolymer (homopolymer A1 and copolymer A3); in the photocuring experiment without adding the prepolymer (homopolymer A1 and copolymer A3) of the invention, the surface pore structure of the membrane M1 is not significantly changed compared with that of the PVDF original membrane, and the change of the water flux is small, which indicates that the crosslinking structure is not obvious.
The experiments fully show that the prepolymer can be used as a cationic photocuring reaction crosslinking agent to endow a photocured coating with a compact crosslinking structure.
3.2. Light curing test of culture dish
3.2.1. Free radical photocuring of the prepolymers of the invention (hyperbranched copolymers A5)
0.2g of A5, 5% by weight (relative to the weight of A5 added) of the free-radical photoinitiator 2-hydroxy-2-methyl-1-phenylacetone were dissolved in 2ml of acetone. Pouring the solution into a culture dish, after the solvent is volatilized, illuminating for 5 minutes under a 240nm ultraviolet lamp, and observing the appearance of the surface of the culture dish.
3.2.2. Cationic photocuring of the prepolymers of the invention (hyperbranched copolymers A5)
0.2g of A5, 3 wt% (based on the weight of A5 added) of a cationic photoinitiator 4- (phenylthio) phenyl diphenylthio
Hexafluorophosphate was dissolved in 2ml acetone. Pouring the solution into a culture dish, after the solvent is volatilized, illuminating for 5 minutes under a 240nm ultraviolet lamp, and observing the appearance of the surface of the culture dish.
3.2.3. Free radical and cationic dual photocuring of the prepolymers of the invention (hyperbranched copolymers A5)
0.2g of A5, 3 wt% (relative to the weight of A5 added) of a cationic photoinitiator 4- (phenylthio) phenyl diphenylthio
Hexafluorophosphate salt and 5 wt% of the radical photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone were dissolved in 2ml of acetone. Pouring the solution into a culture dish, after the solvent is volatilized, illuminating for 5 minutes under a 240nm ultraviolet lamp, and observing the appearance of the surface of the culture dish.
The test results are shown in fig. 8. Fig. 8 is a photograph of the prepolymer solution before photocuring, and the solutions of the three tests were all in a clear and transparent state before light irradiation. After illumination, a white solid was produced on the surface of the dish. The photocuring layer produced by free radical photocuring (3.2.1) and cationic photocuring (3.2.2) curing was thinner, while the dual photocuring (3.2.3) combined with the two curing means produced a cured layer that was significantly denser and thicker.
The hyperbranched copolymer A5 prepared in example 5 according to the invention and the three photocured (3.2.1, 3.2.2 and 3.2.3) products were characterized by infrared. 1630cm -1 The characteristic peak intensity of the double bond of 3.2.1 and 3.2.3 is obviously smaller than the characteristic peak intensity before curing because of the characteristic peak of the carbon-carbon double bond of the hyperbranched copolymer A5; 980cm -1 On the left and right are characteristic peaks of oxetane of hyperbranched copolymer A5, and the intensities of the characteristic peaks at this point of 3.2.2 and 3.2.3 are also significantly reduced. Therefore, the hyperbranched prepolymer containing the oxetanyl group and the unsaturated acrylate double bond can participate in free radical photocuring through the double bond and can also participate in cationic photocuring through the oxetanyl group, and the oxetanyl group and the cationic photocuring can synergistically promote the photocuring effect, so that the formed cured layer is more compact.
Claims (17)
1. An acrylic prepolymer containing an oxetane functional group, characterized in that the side chain of the prepolymer has an oxetane group and the terminal group has an acrylate group.
2. A prepolymer according to claim 1 characterised in that the degree of polymerisation of the prepolymer is in the range 1 to 50, preferably 2 to 18, more preferably 3 to 15; and/or the presence of a gas in the gas,
the weight average molecular weight M of the prepolymer w Is 200-10000Da, preferably 500-8000Da, more preferably 600-5000Da; and/or the presence of a gas in the gas,
the polydispersity index (PDI) of the prepolymer is from 1.0 to 5.0, preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0.
3. A prepolymer according to claim 1 or 2 characterised in that the prepolymer is a homopolymer or copolymer wherein the copolymer is a random, gradient or block copolymer.
4. A prepolymer according to any one of claims 1 to 3, characterised in that the prepolymer is a hyperbranched copolymer, wherein the side chains of the hyperbranched copolymer also have acrylate groups.
5. A prepolymer according to any one of claims 1 to 4 characterised in that the prepolymer is derived from the following monomers:
(A) A monomer of formula 1:
wherein
x is an integer from 1 to 3, preferably x is 1;
R 1 is H or CH 3 Preferably R 1 Is CH 3 (ii) a And
R 2 is H, halogen, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Hydroxyalkyl radical, C 1 -C 6 Alkoxy or C 1 -C 6 A haloalkoxy group; preferably R 2 Is H, halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Hydroxyalkyl radical, C 1 -C 4 Alkoxy or C 1 -C 4 A haloalkoxy group; more preferably R 2 Is H or C 1 -C 4 Alkyl, especially ethyl; and
(B) Optionally other (meth) acrylic or styrenic monomers; and
(C) Optionally di (meth) acrylate ester monomers of glycols.
6. A prepolymer according to claim 5 characterised in that the monomer (A) is (3-ethyloxetan-3-yl) methyl methacrylate.
7. A prepolymer according to claim 5 or 6 characterised in that the monomer (B), if present, is one or more selected from the group consisting of: acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, benzyl acrylate and derivatives thereof, benzyl methacrylate and derivatives thereof, styrene and derivatives thereof; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate are preferred; more preferably methyl methacrylate and/or butyl methacrylate; and/or the presence of a gas in the gas,
if present, the mass ratio of monomer (B) to the sum of the other monomers is 1:1-1:5, preferably 1:1-1:3, more preferably 1:1.
8. A prepolymer according to any one of claims 5 to 7 characterised in that the monomer (C), if present, is one or more selected from the group consisting of: ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate and tripropylene glycol dimethacrylate; preferably ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate and tripropylene glycol dimethacrylate; more preferably ethylene glycol dimethacrylate; and/or
If present, the mass ratio of monomer (C) to the sum of the other monomers is 1:3-1, 20, preferably 1:4-1, 10, more preferably 1:5.
9. A process for the preparation of a prepolymer according to any one of claims 1 to 8 characterised in that monomer (a) and optionally monomer (B) and optionally monomer (C) are subjected to a one-shot Catalysed Chain Transfer Polymerisation (CCTP) reaction in the presence of a chain transfer agent and a free radical initiator.
10. The process according to claim 9, characterized in that the chain transfer agent is one or more selected from the group consisting of: bis [ (difluoroboron) dimethylglyoximato ] cobalt (II), bis [ (difluoroboron) dimethylphenyldioximido ] cobalt (II), bis [ (difluoroboron) diphenylglyoximato ] cobalt (II), bis [ dimethylglyoximato ] cobalt (II), [ meso-tetraphenylporphyrin ] cobalt, tetramethylether-type hematoporphyrin cobalt, tetrafluorophenylporphyrin cobalt, bis [ (difluoroboron) dimethylglyoximato ] isopropylpyridinium cobalt (II), and 2,16-bis (4-butylamido) cobalt phthalocyanine (II), preferably bis [ (difluoroboron) dimethylglyoximato ] cobalt (II) (CoBF); and/or the presence of a gas in the gas,
the chain transfer agent is used in an amount of 0.1 to 100ppm, preferably 1 to 80ppm, more preferably 5 to 50ppm, based on the total weight of the monomers.
11. A process according to claim 9 or 10, characterised in that the free radical initiator is one or more selected from the group consisting of: ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyronitrile formamide, dibenzoyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide, preferably azobisisobutyronitrile; and/or
The free-radical initiators are used in amounts of from 0.1 to 8% by weight, preferably from 0.1 to 4% by weight, more preferably from 0.3 to 2% by weight, based on the total weight of the monomers.
12. Process according to any one of claims 9 to 11, characterized in that the reaction temperature is between 50 and 120 ℃, preferably between 55 and 100 ℃, more preferably between 60 and 80 ℃.
13. The process according to any one of claims 9 to 12, characterized in that the one-step Catalyzed Chain Transfer Polymerization (CCTP) reaction is carried out as a polymerization mode of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or precipitation polymerization.
14. Use of a prepolymer according to any one of claims 1 to 8 or obtained according to the process of any one of claims 9 to 13 in radical curing and/or cationic curing.
15. A photocurable composition comprising the prepolymer as defined in any one of claims 1 to 8 or as obtained according to the process of any one of claims 9 to 13.
16. Cured material obtainable from the photocurable composition of claim 15.
17. A process for preparing a photocurable material comprising irradiating the photocurable composition of claim 15 with ultraviolet light, visible light, or laser light.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20010002423A1 (en) * | 1998-07-09 | 2001-05-31 | Naoki Sugiyama | Oxetane compound, oxetane copolymer, and process for producing the oxetane compound |
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| CN117247534A (en) * | 2023-10-20 | 2023-12-19 | 浙江恒翔新材料有限公司 | Preparation method and application of modified hyperbranched polyether for cutting fluid |
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